KR20230005856A - Curable adhesive composition for multipurpose bonding applications - Google Patents

Abstract

The present invention relates to curable adhesive compositions based on acetoacetate compounds and their use in multipurpose bonding applications. In particular, the present invention relates to curable adhesive compositions based on multifunctional acetoacetate compounds and polyoxyalkylene polyamines.

Description

Curable adhesive composition for multipurpose bonding applications

The present invention relates to curable adhesive compositions based on acetoacetate compounds and their use in multipurpose bonding applications. In particular, the present invention relates to curable adhesive compositions based on multifunctional acetoacetate compounds and polyoxyalkylene polyamines.

Multipurpose adhesives, also known as general purpose adhesives, are used in many substrates encountered in industrial manufacturing or household use, such as paper, cardboard, photos, textiles, leather, felt, bast, cork, film, metals such as aluminum and steel, porcelain, ceramics, glass. , wood, and various plastics such as PVC. Such adhesives are expected to produce an adequate adhesive effect to these various substrates, whose surface structures are chemically and physically different and which generally undergo special surface treatment prior to bonding.

While there are many different classes and types of adhesives used in industry and workplaces, only a few can meet the stringent demands placed on the versatility of multi-purpose adhesives. Among them, polyvinyl acetate and copolymers thereof are widely used.

Demand or versatility represents a particularly difficult selection criterion for adhesive compositions. After all, the adhesive composition should exhibit an equally high affinity for polar and non-polar surfaces. Thus, the statement that a material is suitable for use in an adhesive does not tell the expert whether it can be used in a general purpose adhesive composition as well. Accordingly, efforts are being made to address these needs.

For example, US 6602958 B2 discloses a two-part room temperature curing methacrylate-based adhesive used to bond a variety of materials including thermosetting plastics, thermoplastics, metals, wood, ceramics and other materials and combinations of materials. It is reported to involve a significant improvement in the adhesive's ability to bond certain difficult-to-bond composite materials with minimal required surface preparation.

DE 102009045197 A1 discloses component (a) containing poly(meth)acrylic acid and/or at least one (meth)acrylic acid copolymer, suitable for use as a multipurpose adhesive, and at least one capable of salt formation by releasing a proton in water Disclosed is an aqueous adhesive comprising component (b) containing at least one polyurethane having a component of

US 5270433 A describes (a) polyol mixtures comprising polypropylene glycol, (b) mixtures of polyfunctional isocyanates comprising α,α,α′,α′-tetramethyl xylene diisocyanate, (c) salt formation in aqueous solutions. A universal household adhesive composition comprising a substantially clear, solvent-free, aqueous one-component polyurethane dispersion containing the reaction product of this possible functional component, and (d) optionally a chain extender.

Accordingly, it is an object of the present invention to provide an adhesive composition alternative with a safer toxicity profile for multipurpose bonding applications.

This object is solved by a curable adhesive composition comprising a multifunctional acetoacetate compound and at least two polyoxyalkylene polyamines, which is capable of bonding substrates made of various materials such as metal, wood, plastic, etc. in a fixation time of 5 minutes or less. time, and has excellent adhesion performance.

In one aspect, the present invention relates to a curable adhesive composition comprising:

multifunctional acetoacetate compounds,

polyoxypropylene polyamine, and

A polyoxyalkylene polyamine having an oxyalkylene unit selected from at least two of an oxypropylene unit, an oxyethylene unit, and an oxytetramethylene unit.

In another aspect, the present invention relates to a first part comprising a multifunctional acetoacetate compound and a polyoxypropylene polyamine, and an oxyalkylene selected from at least two of oxypropylene units, oxyethylene units, and oxytetramethylene units A two-part curable adhesive composition comprising a second part comprising a polyoxyalkylene polyamine having monomers.

In another aspect, the present invention relates to a curable adhesive composition or a two-part curable adhesive composition for bonding substrates made of or having a surface of paper, fabric, leather, metal, porcelain, porcelain, glass, wood, or plastic. It's about use.

Further preferred embodiments of the invention are set out in the claims.

In this specification, the terms "one" and "an" and "at least one" are equivalent to the term "one or more" and may be used interchangeably.

As used herein, “one or more” refers to at least one, and includes 1, 2, 3, 4, 5, 6, 7, 8, 9 or more of the recited species. Similarly, “at least one” means one or more, ie 1, 2, 3, 4, 5, 6, 7, 8, 9 or more. “At least one” as used herein with reference to any component refers to the number of chemically distinct molecules, i.e., the number of different types of a stated species, but does not refer to the total number of molecules.

Where reference is made herein to the molecular weight of a polymer or component thereof, such reference refers to the number average molecular weight M _n unless expressly indicated otherwise. The number average molecular weight M _n can be determined by gel permeation chromatography using THF as an eluent. Unless otherwise specified, all molecular weights given are those confirmed by end group analysis. The weight average molecular weight M _w can be determined by GPC as described for M _n .

All percentages given herein with respect to a composition or formulation are relative to the total weight of the composition or formulation unless expressly stated otherwise.

According to the present invention, the curable adhesive composition comprises a multifunctional acetoacetate compound, a polyoxypropylene polyamine, and a polyoxyalkylene unit having oxyalkylene units selected from at least two of oxypropylene units, oxyethylene units, and oxytetramethylene units. including len polyamines. The inventors have surprisingly discovered that the curable adhesive composition is suitable for bonding various types of substrates such as paper, textiles, leather, metal, porcelain, porcelain, glass, wood, or plastics.

The developed curable adhesive composition has excellent adhesion properties for multipurpose bonding and a mild toxicity profile compared to standard epoxy- or (meth)acrylate-based formulations. Based on acetylacetonate resin curing with polyether amine curing agents, formulations with set times of 5 minutes or less that can be applied from, for example, a two-part cartridge and cured to strong polymers have been developed. Strong adhesive and cohesive forces have been found for the bonding of metals, various plastics and wood. The rheological behavior and mixing ratio can be tuned by fillers, and improved mechanical resistance has been observed with the incorporation of filler particles into formulations.

The curable adhesive composition is formulated to provide a cured product having a lap shear strength of at least 10 MPa for bonding steel substrates.

The curable adhesive composition is formulated to provide a cured product having a lap shear strength of 10 MPa or more in bonding an aluminum substrate.

The curable adhesive composition is formulated to provide a cured product having a lap shear strength of 7 MPa or more for bonding wood substrates.

The curable adhesive composition is formulated to provide a cured product having a lap shear strength of at least 5 MPa for bonding a polycarbonate (PC) substrate.

The curable adhesive composition is formulated to provide a cured product having a lap shear strength of at least 3 MPa for bonding a polyvinyl chloride (PVC) substrate.

The curable adhesive composition is formulated to provide a cured product having a lap shear strength of at least 4 MPa for bonding a poly(methyl methacrylate) (PMMA) substrate.

The curable adhesive composition is formulated to provide a cured product having a lap shear strength of at least 3 MPa for bonding an acrylonitrile-butadiene-styrene (ABS) substrate.

In addition, curable adhesive compositions have other advantages. For example, the adhesive composition is solvent-free, catalyst-free, has a workable viscosity and pot life, and cures rapidly even at room temperature. Finally, the curable adhesive composition provides a strong adhesive bond that is resistant to humidity and chemicals such as acetone, ethyl acetate, 2-propanol, methyl ethyl ketone, ethanol and toluene.

According to the present invention, the multifunctional acetoacetate compound may have at least 2 acetoacetoxy groups, preferably 2 to 10 acetoacetoxy groups, more preferably 2 to 4 acetoacetate groups. Thus, this component may include a single compound having at least two acetoacetoxy groups or a mixture of two or more compounds each having at least two acetoacetoxy groups. Each of these compounds will preferably be characterized by a number average molecular weight (M _n ) of less than 12000 g/mol, for example less than 10000 g/mol or less than 6000 g/mol.

In a preferred embodiment, the curable adhesive composition comprises at least one acetoacetylated polyol, which can be obtained according to the equation (reaction 1):

In the formula: R is a C ₁ -C ₁₂ alkyl group;

L represents the backbone structure of the polyol;

q ≥ 2.

Reaction 1 above can be described as transesterification - or more specifically transacetylation - of a polyol with an acetoacetate compound as defined in formula (I) below:

In the formula, R is the above C ₁ -C ₁₂ alkyl group. More typically, the constituent alkyl group R has 1 to 8, preferably 1 to 6 carbon atoms. Exemplary alkyl acetoacetates include: t-butyl acetoacetate; isobutyl acetoacetate; n-butyl acetoacetate; isopropyl acetoacetate; n-propyl acetoacetate; ethyl acetoacetate; and, methyl acetoacetate. t-Butyl acetoacetate is preferred herein.

The polyol of reaction 1 above is represented herein by formula (II):

L-(OH) _q Formula (II)

In the equation, q ≥ 2, and L represents the backbone structure. Such polyols (II) may optionally contain heteroatoms in their backbone or in pendant side chains. Polyol (II) may also be a monomeric polyhydric alcohol or may have an oligomeric or polymeric backbone. Regardless, polyol (II) has a number average molecular weight (M _n ) of less than 12000 g/mol; It is preferred that the hydroxyl functionality, q, is from 2 to 10, preferably from 2 to 4.

In one embodiment, the curable adhesive composition comprises an acetoacetylated polyol obtained from a monomeric polyhydric alcohol. Examples of suitable monomeric polyhydric alcohols include, but are not limited to: 1,2-butanediol; 1,3-butanediol; 1,4-butanediol; 2,3-butanediol; 2,4-pentanediol; butyl ethyl propane diol; 1,4-hexanediol; 1,4-cyclohexane dimethanol; pentaerythritol; dipentaerythritol; trimethylolethane; trimethylolpropane; ditrimethylolpropane; tricyclodecane dimethanol; hydroquinone bis(2-hydroxyethyl) ether; alkylene glycols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, pentamethylene glycol, hexamethylene glycol, hexylene glycol and neopentyl glycol; glycerol; castor oil; castor wax; sugars such as glucose, sucrose, fructose, raffinose, maltodextrose, galactose, xylose, maltose, lactose, mannose and erythrose; sugar alcohols such as erythritol, xylitol, maltitol, mannitol and sorbitol; and hydroxyalkylated aliphatic diamines such as o,o'-bis(diethanolaminomethyl)-p-nonylphenol, N,N,N,N'-tetra(2-hydroxypropyl)ethylenediamine (Quadrol L, available from BASF) and N,N,N,N-tetra(2-hydroxyethyl)ethylenediamine. In a preferred embodiment, the multifunctional acetoacetate compound is glycerol, trimethylolpropane, ethanol isosorbide, neopentylglycol, pentaerythritol, di-methylolpropane, di-pentaerythritol, propoxylated monosaccharides, trimethylol It is an acetoacetylated polyol obtained from ethane, and combinations thereof.

The present invention also does not exclude that such polyfunctional acetoacetate compounds include acetoacetylated polyols obtained from oligomeric or polymeric polyhydric alcohols. In particular, the polyol (II) may be selected from the group consisting of: polyoxyalkylene polyols, also called polyether polyols; polyester polyols including polycaprolactone polyols; polyesteramide polyols; polycarbonate polyols; polybutadiene polyol; polyurethane polyols; polyacrylate polyols; and combinations thereof. Preferably, these oligomeric or polymeric polyols will be characterized by a number average molecular weight (M _n ) of at most 10000 g/mol, preferably from 250 to 6000 g/mol. Also of particular interest is the use of one or more polyether polyols or polyester polyols as starting materials. And a commercial example of a polyether polyol is Voranol CP260 (available from DowDuPont).

As is known in the art, polyester polyols are prepared from the condensation reaction of a polybasic carboxylic acid or anhydride with a stoichiometric excess of a polyhydric alcohol, or from mixtures of polybasic carboxylic acids, monobasic carboxylic acids and polyhydric alcohols. It can be. Suitable polybasic carboxylic acids and anhydrides for use in preparing the polyester polyols include those having 2 to 18 carbon atoms, and especially those having 2 to 10 carbon atoms. Non-limiting examples of such polybasic carboxylic acids and anhydrides include: adipic acid; glutaric acid; succinic acid; malonic acid; pimelic acid; sebacic acid; suberic acid; azelaic acid; 1,4-cyclohexane dicarboxylic acid; phthalic acid; phthalic anhydride; isophthalic acid; terephthalic acid; tetrahydrophthalic acid; hexahydrophthalic acid; and combinations thereof. Monobasic carboxylic acids that may be used include those having 1 to 18 carbon atoms, or preferably 1 to 10 carbon atoms, among which examples may be mentioned: formic acid; acetic acid; propionic acid; butyric acid; valeric acid; caproic acid; caprylic acid; capric acid; lauric acid; myristic acid; palmitic acid; stearic acid; and combinations thereof. Suitable polyhydric alcohols have 2 to 18 carbon atoms, and preferably 2 to 10 carbon atoms. Exemplary polyhydric alcohols include, but are not limited to: ethylene glycol; propylene glycol; hexane-1,6-diol; trimethylol propane; glycerol; neopentyl glycol; pentaerythritol; butylene glycol; 2-methyl-1,3-propane diol; hexylene glycol; and combinations thereof.

Polyether polyols can be prepared by methods known in the art, such as the reaction of an alkene oxide with a polyvalent starter molecule in the presence of a suitable catalyst such as an alkali metal hydroxide, alkali metal alkoxide or antimony pentachloride. Examples of alkene oxides include: tetrahydrofuran; ethylene oxide; 1,2-propylene oxide; 1,2- and 2,3-butylene oxide; and styrene oxide. And examples of suitable starter molecules include, but are not limited to: water; ethylene glycol; 1,2- and 1,3-propanediol; 1,4-butanediol; diethylene glycol; and, trimethylol-propane. Preferred polyether polyols for use herein are: poly(propylene oxide) polyols; poly(ethylene oxide) polyols; PTMEG; and mixtures thereof.

Polycarbonate polyols for use herein may be selected from, but are not limited to, polycarbonate diols. These polycarbonate diols can be prepared by reaction of diols with dialkyl or diaryl carbonates or phosgene. The reactant diol may be selected from, but is not limited to: 1,2-propanediol; 1,3-propanediol; 1,4-butanediol; 1,5-pentanediol; 1,6-hexanediol; diethylene glycol; trioxyethylene glycol; and mixtures thereof. An exemplary diaryl carbonate is diphenyl carbonate.

The transesterification (transacetylation) reaction 1 can be carried out by conventional methods as known in the field of polymer chemistry. In this regard, reference may be made in particular to Witzman et al. "Comparison of Methods for the Preparation of Acetoacetylated Coating Resins", Journal of Coatings Technology, Vol. 62, no. 789, October 1990; and, Witzeman et al. “Transacetoacetylation with tert-butyl acetoacetate: Synthetic Applications”, J. Org. Chemistry 1991, 56, 1713-1718. Typically, the reaction of an oligomeric or polymeric polyol with acetoacetate is carried out by mixing the polyol and acetoacetate in a suitable vessel at an elevated temperature, for example from 50 to 200° C., or from 80 to 150° C., with or without a solvent. will entail; Preferably, the reaction is conducted in the absence of a solvent. The reaction is conducted until completion by distilling off the alcohol (R-OH) formed under reduced pressure. In addition, the reaction can be carried out in the presence of a catalytic amount of a transesterification catalyst, suitable examples of which include, but are not limited to, calcium acetate, zinc acetate, bismuth acetate, lead oxide, and trichloroacetic acid.

Although the products of the transacetylation reaction described above may be used directly in the multipurpose adhesive composition of the present invention, the reaction products may first be equally isolated and purified using methods known in the art. In this connection, extraction, evaporation, distillation and chromatography may be mentioned as suitable techniques.

According to the present invention, the curable adhesive composition also includes a polyoxypropylene polyamine. Polyoxypropylene polyamine refers to a polyamine having only oxypropylene units in its backbone structure.

In one preferred embodiment, the polyoxypropylene polyamine is selected from polyoxypropylene diamines, polyoxypropylene triamines, and combinations thereof.

Examples of polyoxypropylene diamines are those represented by formula (1)

In the formula, x is 2 to 100, preferably 2 to 80.

Preferably, the polyoxypropylene diamine has a number average molecular weight of 100 to 5,000, more preferably 200 to 4,000.

Such polyoxypropylene diamines are commercially available from Huntsmann as Jeffamine D series polyether polyamines such as D-230, D-400, D-2000 and D-4000.

An example of polyoxypropylene triamine is represented by formula (2)

In the formula, n is 0 to 6, w, y and z are each independently 1 to 100, more preferably 1 to 80, and the sum of w, y and z is 3 to 100, preferably 5 to 85, R ₁ is hydrogen or a linear or branched C ₁ to C ₁₆ alkyl group, preferably hydrogen or a linear or branched C ₁ to C ₈ alkyl group.

Preferably, the polyoxypropylene triamine has a number average molecular weight of 100 to 8,000, more preferably 200 to 6,000.

Such polyoxypropylene triamines are commercially available from Huntsmann as Jeffamine T series polyether polyamines such as T-403, T-3000 and T-5000.

According to the present invention, the curable adhesive composition also includes a polyoxyalkylene polyamine having oxyalkylene units selected from at least two of oxypropylene units, oxyethylene units, and oxytetramethylene units.

In one embodiment, the polyoxyalkylene polyamine has oxypropylene units and oxyethylene units in the backbone structure. Such polyoxyalkylene polyamines can be represented by formula (3)

In the formula, a is 0 to 10, b is 2 to 60, c is 0 to 10, and the sum of a and c is 2 to 20.

Preferably, such polyoxyalkylene polyamines having oxypropylene units and oxyethylene units have a number average molecular weight of 100 to 5,000, more preferably 200 to 3,000.

Such polyether polyamines are commercially available from Huntsmann as the Jeffamine ED series polyether polyamines such as ED-600, ED-900 and ED-2003.

In another embodiment, the polyoxyalkylene polyamine has oxypropylene units and oxytetramethylene units in its backbone structure.

Preferably, such polyoxyalkylene polyamines having oxypropylene units and oxytetramethylene units have a number average molecular weight of 100 to 3,000, more preferably 200 to 2,000.

Such polyether polyamines are commercially available from Huntsmann as the Jeffamine THF series polyether polyamines such as THF-100, THF-140 and THF-170.

Optionally, the curable adhesive composition herein comprises at least one amine cure accelerator having 1 to 10, for example 2 to 6 or 2 to 4 primary and/or secondary amino groups according to formula (III) below: :

R ² R ³ NH Formula (III)

In the formula: R ² is hydrogen or a C ₁ -C ₆ alkyl group;

R ³ is a hydrocarbyl group having up to 36 carbon atoms containing an aromatic group, which hydrocarbyl group is optionally substituted with one or more -NHR ² groups, with one or more O atoms and/or with one or more -N(R ⁴ )-, wherein R ⁴ is a hydrogen atom; or,

R ³ is a C ₁ -C ₃₆ aliphatic group, optionally substituted with one or more -NHR ² groups, and optionally further interrupted by one or more O atoms and/or with one or more -N(R ⁴ )- groups, wherein R ⁴ is a hydrogen atom;

R ² and R ³ together with the N-atom to which they are attached may form a ring.

For completeness, it will be understood that where R ² and R ³ form a ring, such ring may be a heterocycle and may contain one or more nitrogen atoms.

Good results have also been obtained when the reactant amine according to formula (III) is characterized by: R ² is hydrogen; R ³ is a C ₁ to C ₃₆ alkyl group, preferably a C ₁ to C ₁₂ alkyl group, optionally substituted with at least one -NHR ² group and optionally interspersed with one or more -N(R ⁴ )- groups; Here, R ⁴ is a hydrogen atom. Exemplary di-primary amines of this embodiment include: tetramethylene diamine; pentamethylene diamine; hexamethylene diamine; octamethylene diamine; and, dodecamethylene diamine. Exemplary primary-secondary diamines of this embodiment include: N-methylethylenediamine; N-ethylethylenediamine; N-methyl-1,3-diaminopropane; 2-(isopropylamino)ethylamine; N-propylethylenediamine; N-propyl-1,3-propanediamine; N-cyclohexyl-1,3-propanediamine; 4-(aminomethyl)piperidine; 3-(aminomethyl)piperidine; 2-(aminomethyl)piperidine; and, 4-aminopiperidine.

Additional exemplary commercial amines for use in the present invention include, but are not limited to: 2-methyl-1,5-diaminopentane, available as Dytek A from Invista Arpadis; 1,2-diaminocyclohexane available as an isomeric mixture of Dytek DCH-99 from Invista Arpadis; N,N'-dimethyl hexanediamine (MAHMA) available from Sigma-Aldrich; fatty acid dimer diamines available from Croda as Priamine 1071, 1073, 1074 and 1075; phenalkamine available as Cardolite NX-5608, NX-5607 and LITE 3060 from Cardolite Corporation; Polyethyleneimine (PEI) available under the trade name Lupasol G 20 (anhydrous), and Lupasol FG available from BASF, and isophorone diamine available from Sigma-Aldrich.

And additional exemplary amines suitable for use in the compositions of the present invention include: piperidine and pyrrolidine.

In certain circumstances it is advantageous for the amine cure accelerator to include a primary amine according to formula (III) characterized in that R ² is hydrogen and R ³ is a C ₁ to C ₁₂ alkyl group, preferably a C ₁ to C ₆ alkyl group. can do. Exemplary amines of this type include: n-butylamine; n-hexylamine; n-octylamine; n-decylamine; and, n-dodecylamine.

In one preferred embodiment, the amine cure accelerator is a cycloaliphatic amine, preferably isophorone diamine, methane diamine, 1,2-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4-diamino Cyclohexane, 1,3-di(aminomethyl)cyclohexane, 4,4'-methylene dicyclohexylamine, 4,4'-diaminodicyclohexylmethane, 3,3'-dimethyl-4,4'- diaminodicyclohexyl-methane, and combinations thereof.

If present, the molar equivalent ratio of amine groups in the amine cure accelerator to amine groups in the polyether polyamine is from 1:10 to 10:1, preferably from 1:5 to 5:1, more preferably from 1:3 to 1:3. It is in the 3:1 range.

It is noted that the compositions of the present invention may include amines from polyether polyols and amine cure accelerators (if present) in large amounts or the acetoacetates above. Compositions of the present invention may be characterized, for example, by molar equivalent ratios of acetoacetate to amine ranging from 1:10 to 10:1 in a wide range. However, the total amount of amine in the composition of the present invention is generally selected such that the molar equivalent ratio of acetoacetate to amine is in the range of 2:1 to 1:2, for example in the range of 1.2:1 to 0.8:1. Thus, while it is preferred that 1 mole of amine be available for 1 equivalent of acetoacetate in the composition, dispersion over this preferred 1:1 equivalent ratio may be tolerated.

An advantage of the chemistry of the curable composition of the present invention is that its cure rate can be tuned or controlled to control the rate of development of the mechanical properties of the cured material on various types of substrates. For example, the rapid curing reaction and concomitant rapid development of these mechanical properties can be advantageous in multi-purpose bonding applications.

To form a multipurpose curable adhesive composition, the reactive components are brought together and mixed in a manner that induces its curing. More particularly, the ingredients may be mixed in predetermined amounts by hand, by machine, by co-extrusion or by any other means capable of ensuring their delicate and highly uniform mixing. Upon initial mixing—by “initial” herein is meant one minute or less after the components are combined—the curable adhesive composition is a liquid or paste at room temperature. This fact however does not exclude that the mixing temperature is above room temperature, for example up to 15° C. above room temperature.

The curable adhesive composition may, of course, contain additional components and additives. However, the adhesive composition must be formulated to exhibit an initial viscosity suitable for a wide range of paste or liquid materials. In the case of an adhesive composition containing no filler, it is in the range of less than 30000 mPa·s, preferably less than 15000 mPa·s, and more preferably less than 7500 mPa·s at 25°C. In the case of an adhesive composition comprising a filler, it is in the range of less than 2000 Pa·s, preferably less than 1000 Pa·s, more preferably less than 500 Pa·s.

Independently or in addition to the above viscosity characteristics, the curable adhesive composition should be formulated so as to be bubble free upon mixing and subsequent curing. Moreover, the curable adhesive composition should further be formulated to exhibit at least one, preferably at least two, and most preferably all of the following properties: i) hold strength after curing the composition for 5 minutes; ii) a maximum exothermic temperature of 120°C or less, preferably 100°C or less, more preferably 80°C or less; and, iii) a Shore A hardness of at least 50, preferably at least 60, more preferably at least 70 after curing and storage for 7 days at room temperature and 50% relative humidity.

The composition of the present invention may not contain a solvent. Alternatively, the composition may include one or more solvents, at least one of which is preferably miscible with water. It is therefore believed that the compositions of the present invention may be characterized as solvent systems consisting of two or more solvents that are miscible with water. Equally, the composition of the present invention may be characterized by a solvent system composed of at least one solvent that is immiscible with water and at least one solvent that is miscible with water. For completeness, the term "immiscible" as used herein means that the two phases are present in some proportion.

Non-limiting examples of solvents that are miscible with water include, but are not limited to, acetic acid, acetone, acetonitrile, dimethylformamide, dimethyl sulfoxide, dioxane, ethanol, methanol, n-propanol, isopropanol, and tetrahydrofuran. does not Non-limiting examples of solvents that are immiscible with water include benzene, n-butanol, butyl acetate, carbon tetrachloride, chloroform, cyclohexane, 1,2-dichloroethane, dichloromethane, ethyl acetate, di-ethyl ether, heptane, hexane, methyl-1-butyl ether, methyl ethyl ketone, pentane, di-isopropyl ether, toluene, trichloromethane, xylene, and combinations thereof.

If used, the amount of solvent present in the composition can be determined based on conventional practical considerations. Generally, however, the volume to mass ratio of solvent to acetoacetate functionalized compound(s) will be in the range of 1:1 to 100:1. In some embodiments, the volume to mass ratio of solvent to acetoacetate functionalized compound(s) may range from 1:1 to 50:1.

The composition of the present invention may of course also contain standard additives such as pigments, fillers, plasticizers, surface levelers, foam inhibitors, rheology modifiers, catalysts, antioxidants, tackifiers, adhesion promoters, flame retardants and UV-stabilizers. there is. Selection of suitable additives is limited only in that they must be compatible with the other components of the composition and not detrimental to the use of the composition in multipurpose bonding applications.

If fillers are used, they should typically be included in an amount of up to 75% by weight based on the weight of the composition, for example up to 50% or up to 30% by weight. Suitable for use as fillers herein are, for example, chalk, lime powder, precipitated and/or pyrogenic silicic acid, zeolites, bentonites, magnesium carbonate, diatomaceous earth, alumina, clay, talc, titanium oxide, iron oxide, zinc oxide, sand, quartz, flint, mica, glass powder, aluminum trihydroxide, magnesium hydroxide and other ground mineral substances. Organic fillers, especially carbon black, graphite, rubber particles, wood fibers, wood flour, sawdust, cellulose, melamine, cotton, pulp, wood chips, chopped straw, rice hulls, ground walnut shells, and other hard fibers can also be used Short fibers such as glass fibers, glass filaments, polyacrylonitrile, carbon fibers, Kevlar fibers or polyethylene fibers may also be added. Likewise, aluminum powder is suitable as a filler.

In certain embodiments, plasticizers may be included to mitigate the softness and flexibility of the cured curable adhesive composition. The one or more plasticizers in this case are vegetable oils; mineral oil; soybean oil; terpene resins; aromatic esters such as dioctyl phthalate, diundecyl phthalate, tricresyl phosphate and triisononyl melittate; linear esters such as di-tridecyl adipate; chlorinated paraffin; aromatic and naphthenic process oils; alkyl naphthalenes; and low molecular weight polyisoprene, polybutadiene, mono-functional and long-chain containing amine or polybutylene resins. Typically, the amount of plasticizer should be 0 to 20% by weight, preferably 0 to 10% or 0 to 5% by weight based on the total weight of the multipurpose adhesive composition.

The curing reaction of the composition may be accelerated. Known catalysts include, for example, stannous octoate, stannous dioleate, stannous palmitate, stannous oxalate, boron trifluoride etherate and Bronsted acid. Also, if used, the amount of catalyst - as determined in the absence of any applicable support - should be from 0.001 to 5% by weight, preferably from 0.01 to 2% by weight, based on the total weight of the reactant amines used. However, it is highly preferred that the compositions of the present invention are free of catalysts.

Organofunctional silanes such as mercaptofunctional, epoxyfunctional and especially aminofunctional silanes can preferably be used as adhesion promoters to improve adhesion to metals. Examples of mercaptofunctional silanes are 3-mercaptopropyl trimethoxysilane or 3-mercaptopropyl triethoxysilane or their alkyl dimethoxy or alkyl diethoxy analogues. As examples of aminofunctional silanes, mention may be made of 3-aminopropyl alkoxysilane, 2'-aminoethyl-3-aminopropyl alkoxysilane. Epoxyfunctional silanes can be selected from a number of compounds. For example, the following may be mentioned: 3-glycidyloxymethyl trimethoxysilane, 3-glycidyloxymethyl triethoxysilane, 3-glycidoxymethyl tripropoxysilane, 3-glycy Doxymethyl tributoxysilane, 2-glycidoxyethyl trimethoxysilane, 2-glycidoxyethyl triethoxysilane, 2-glycidoxyethyl tripropoxysilane, 2-glycidoxyethyl tributoxysilane , 2-glycidoxyethyl trimethoxysilane, 1-glycidoxyethyl triethoxysilane, 1-glycidoxyethyl tripropoxysilane, 1-glycidoxyethyl tributoxysilane, 3-glycidoxy propyl trimethoxysilane, 3-glycidoxypropyl triethoxysilane, 3-glycidoxypropyl tripropoxysilane, 3-glycidoxypropyl tributoxysilane, 2-glycidoxypropyl trimethoxysilane, 2-glycidoxypropyl triethoxysilane, 2-glycidoxypropyl tripropoxysilane, 2-glycidoxypropyl tributoxysilane, 1-glycidoxypropyl trimethoxysilane, 1-glycidoxypropyl Triethoxysilane, 1-glycidoxypropyl tripropoxysilane, 1-glycidoxypropyl tributoxysilane, 3-glycidoxybutyl trimethoxysilane, 4-glycidoxybutyl triethoxysilane, 4 -Glycidoxybutyl tripropoxysilane, 4-glycidoxybutyl tributoxysilane, 4-glycidoxybutyl trimethoxysilane, 3-glycidoxybutyl triethoxysilane, 3-glycidoxybutyl tri Propoxysilane, 3-alpropoxybutyl tributoxysilane, 4-glycidoxybutyl trimethoxysilane, 4-glycidoxybutyl triethoxysilane, 4-glycidoxybutyl tripropoxysilane, 1- Glycidoxybutyl trimethoxysilane, 1-glycidoxybutyl triethoxysilane, 1-glycidoxybutyl tripropoxysilane, 1-glycidoxybutyl tributoxysilane, (3,4-epoxycyclohexyl ) Methyl trimethoxysilane, (3,4-epoxycyclohexyl)methyl trimethoxysilane, (3,4-epoxycyclohexyl)methyl tripropoxysilane, (3,4-epoxycyclohexyl)methyl tributoxy Silane, (3,4-epoxycyclohexyl)ethyltrimethoxysilane, (3,4-epoxycyclohexyl)ethyltriethoxysilane, (3,4-epoxycyclohexyl)ethyltripropoxysilane, (3, 4-epoxycyclohexyl)ethyl tributoxysilane, (3, 4-epoxycyclohexyl)propyl trimethoxysilane, (3,4-epoxycyclohexyl)propyl triethoxysilane, (3,4-epoxycyclohexyl)propyl tripropoxysilane, (3,4-epoxycyclohexyl) )Propyl tributoxysilane, (3,4-epoxycyclohexyl)butyl trimethoxysilane, (3,4-epoxycyclohexyl)butyl triethoxysilane, (3,4-epoxycyclohexyl)butyl tripropoxy Silane, (3,4-epoxycyclohexyl)butyl tributoxysilane. The adhesion promoter is preferably used in an amount of 0.1 to 10% by weight, preferably 0.5 to 4% by weight, particularly preferably 0.5 to 2% by weight in the composition.

A flame retardant may be added to the adhesive composition according to the present invention to improve the performance of the cured product, especially when used for wood bonding. Examples of flame retardants include ammonium polyphosphate, triphenylphosphine oxide, aluminum triethyl phosphinate, zinc diethyl phosphinate, melamine cyanurate, melamine phosphate, melamine polyphosphate, melamine pyrophosphate, melamine ammonium polyphosphate, Melamine Ammonium Pyrophosphate, Melamine Borate, Triphenyl Phosphate, Resorcinol Bis-(Diphenyl Phosphate), Bisphenol A-bis-(Diphenyl Phosphate), Resorcinol-bis-(2.6-disylylenylphosphate) , aluminum hydroxide, aluminum hydroxide, magnesium dihydroxide, zinc oxide, molybdenum trioxide, antimony oxide, aluminum trihydroxide, zinc borate, calcium silicate, magnesium silicate, calcium sulfate, magnesium carbonate, dihydroxyphosphaphenanthrene, Hydroxaphosphaphenanthrene-hydroquinone, potassium diphenyl sulfone sulfonate, poly methyl phenyl siloxane, potassium-butyl perfluoro sulfonate and mixtures thereof. The flame retardant is preferably used in the composition in an amount of 0.1 to 20% by weight, preferably 0.5 to 15% by weight, particularly preferably 0.5 to 10% by weight.

In another aspect, the present invention relates to a first part comprising a multifunctional acetoacetate compound and a polyoxypropylene polyamine, and an oxyalkylene selected from at least two of oxypropylene units, oxyethylene units, and oxytetramethylene units A two-part curable adhesive composition comprising a second part comprising a polyoxyalkylene polyamine having monomers.

The ingredient(s) in each part are stored in separate containers (parts) from the other parts until the contents of all containers are mixed together to form a mixture of adhesive composition prior to application. Upon application and curing, a solid material is formed in the bonding area.

Another embodiment of the present invention is a method of adhering substrates to each other using the curable adhesive composition of the present invention. In this embodiment, a curable composition is applied to a first substrate. Methods of application can be applied in a number of ways known to those skilled in the art to form a continuous or discontinuous film of the composition as desired (e.g. brushing, spraying, roller coating, rotogravure coating, flexographic coating, flow coating, dipping and any of these). combination) can be implemented. In some embodiments, the curable composition will be applied at ambient temperature (approximately 25° C.); Alternatively, the curable composition may be applied at an elevated temperature.

After the composition is applied to a first substrate, it can then be contacted with another substrate to form a composite. The so-formed composite may optionally be subjected to applied pressure, such as passing it through rollers to achieve increased contact of the composition with the substrate. In another embodiment of the invention, the composition can be applied simultaneously or sequentially to both surfaces of a first substrate and then the composition is simultaneously or sequentially bonded to two additional substrates, which may be the same or different. It is further contemplated that the composite structure may be sequentially bonded to other substrate(s) using the composition of the present invention, or a different composition before or after the processes described herein. The first and second substrates to be joined in the method of the present invention may be the same or different, for example paper, textile, leather, metal (such as aluminum and steel), porcelain, porcelain, glass, wood, or plastic (such as PP, PC, PVC, etc.), which may have a smooth or structured surface and may be provided in the form of rolls, sheets, films, foils, and the like.

In some embodiments of the invention, the substrate is relatively thin and flat, and the resulting composite is called a laminate. The substrate may consist of a multi-layer laminate structure based on polyalkylenes such as polyethylene, and polypropylene, polyesters, and polyamides (nylon), metallized polypropylene, aluminum foil, and the like. Examples of two-ply laminate structures include polypropylene/polypropylene, polyester/nylon, polyester/polyethylene, polypropylene/metallized polypropylene, polypropylene/aluminum foil, polyester/aluminum foil, polyamide/aluminum foil, and the like. include

It is believed that the curable adhesive composition of the present invention will undergo a chemical reaction referred to herein as "cure". Although the present invention is not limited to any particular theory, it is believed that curing begins when the curable composition is formed, continues at least to the end of the pot life, and may continue thereafter. In some embodiments, prior to the end of pot life, a layer of curable adhesive composition will be applied to the substrate. In some of these embodiments, at least one additional substrate will be in contact with the layer of curable mixture; Often, an additional substrate will come into contact with the layer of curable adhesive composition prior to the end of its pot life. Thus, in some embodiments, curing will not be complete until after the curable adhesive composition and the substrate have come into contact. It is believed that the cured product will form useful adhesive bonds between substrates.

While the present invention is particularly useful as an adhesive, it is believed that the present invention is also applicable to coatings, polymeric foams, sealants, and elastomers. When used as a coating, the curable adhesive composition will be applied to a substrate and then cured, and no additional substrate will come into contact with the curable mixture. When used as a sealant, foam or elastomer, the curable adhesive composition can be placed in a mold or on a release surface and cured, for example; The cured mixture can then be removed from the mold or release surface and used as intended.

Various features and implementations of this disclosure are described in the following examples, which are intended to be representative and not limiting.

Example

matter

Jeffamine D-230 is a polyoxypropylene diamine with a number average molecular weight of about 230 from Huntsmann.

Jeffamine T-403 is a polyoxypropylene triamine with a number average molecular weight of about 440 from Huntsmann.

Jeffamine ED-600 is a polyoxypropylene polyoxyethylene diamine with a number average molecular weight of about 600 from Huntsmann.

Jeffamine ED-900 is a polyoxypropylene polyoxyethylene diamine with a number average molecular weight of about 900 from Huntsmann.

Jeffamine THF100 is a polyoxypropylene polyoxytetramethylene diamine with a number average molecular weight of about 1000 from Huntsmann.

Priamine 1071 is a dimer fatty acid diamine from Croda.

Jeffamine EDR148 is a diamine with the following structure from Huntsmann.

Dytek DCH-99 is a 1,2-diaminocyclohexane from Invista Arpadis.

(3-aminopropyl)trimethoxysilane is an adhesion promoter from Alfa Aesar.

Omya BLH is ground pig calcium carbonate from Omya.

Aerosil R202 is a hydrophobic fumed silica from Evonik.

Test Methods

Lap Shear Strength

Samples were prepared from two 25 mm wide substrates with a 10 mm overlap. The samples were clamped in place and allowed to cure for 2 days at room temperature before testing. Testing was performed using a Zwick/Roell Z050 pulling at a speed of 10 mm/min.

fixed strength

The holding strength was evaluated as "pass" if the sample did not separate under its own weight when the clamps of the overlap shear sample were removed after 5 minutes curing.

solvent resistance

A two-component formulation of bulk polymer was prepared by mixing all components and curing at room temperature for 7 days. Solvent resistance was tested using a paper tissue soaked in different solvents and rubbed back and forth several times over the surface of the cured bulk polymer. Solvent resistance was evaluated as “pass” when no change in the polymer surface was observed.

Synthesis of trimethylolpropane triacetoacetate

The synthesis of trimethylolpropane triacetoacetate (AATMP) was carried out according to literature procedure WO 2019/120923A1 with minor modifications. A 500 mL 3 neck round bottom flask was charged with trimethylolpropane or pentaerythritol (1 eq.) and TBAA (1.1 eq.). A Y-adapter, mechanical stir bar and reflux condenser were then fitted to the respective necks of the flasks. On the Y-adapter, I adjusted the thermocouple and nitrogen connector. The temperature was set at 140 °C under a nitrogen atmosphere (reflux reached 92 °C in approximately 4 h). Thereafter, distillation was performed at atmospheric pressure for 8 hours while gradually raising the temperature to 140°C. Finally, when the distillation was stopped, distillation was conducted at 140° C. under reduced pressure from 900 mbar to 400 mbar for 2 hours. The reaction formula is shown below.

Example 1

0.175 eq (20.83 g) Jeffamine D230, 0.65 eq (37.11 g) 1,2-diaminocyclohexane, 0.15 eq (46.65 g) Jeffamine ED600 and 0.025 eq (4.48 g) (3-aminopropyl)trimethoxysilane Mix in a PP speed mixer cup. Then 148.09 g Omya BLH and 16.45 g Aerosil R202 were added and mixed in a mixer cup. Finally, 1 equivalent (128.80 g) of AATMP was added and mixed in a mixer cup. The mixture was then mixed in a speed mixer at 3500 rpm for 30 seconds to obtain an adhesive composition.

Example 2

0.175 eq (27.65 g) Jeffamine T403, 0.65 eq (37.11 g) 1,2-diaminocyclohexane, 0.15 eq (46.65 g) Jeffamine ED600 and 0.025 eq (4.48 g) (3-aminopropyl)trimethoxysilane Mix in a PP speed mixer cup. Then 152.37 g Omya BLH and 16.93 g Aerosil R202 were added and mixed in a mixer cup. Finally, 1 equivalent (128.80 g) of AATMP was added and mixed in a mixer cup. The mixture was then mixed in a speed mixer at 3500 rpm for 30 seconds to obtain an adhesive composition.

Example 3

0.175 eq (20.83 g) Jeffamine D230, 0.65 eq (37.11 g) 1,2-diaminocyclohexane, 0.15 eq (74.03 g) Jeffamine ED900 and 0.025 eq (4.48 g) (3-aminopropyl)trimethoxysilane Mix in a PP speed mixer cup. Then 165.13 g Omya BLH and 18.34 g Aerosil R202 were added and mixed in a mixer cup. Finally, 1 equivalent (128.80 g) of AATMP was added and mixed in a mixer cup. The mixture was then mixed in a speed mixer at 3500 rpm for 30 seconds to obtain an adhesive composition.

Example 4

0.175 eq (20.83 g) Jeffamine D230, 0.65 eq (37.11 g) 1,2-diaminocyclohexane, 0.15 eq (76.43 g) Jeffamine THF100 and 0.025 eq (4.48 g) (3-aminopropyl)trimethoxysilane Mix in a PP speed mixer cup. Then 166.63 g Omya BLH and 18.51 g Aerosil R202 were added and mixed in a mixer cup. Finally, 1 equivalent (128.80 g) of AATMP was added and mixed in a mixer cup. The mixture was then mixed in a speed mixer at 3500 rpm for 30 seconds to obtain an adhesive composition.

Example 5

0.15 eq (18.30 g) Jeffamine D230, 0.57 eq (32.61 g) 1,2-diaminocyclohexane, 0.25 eq (77.75 g) Jeffamine ED600 and 0.025 eq (4.48 g) (3-aminopropyl)trimethoxysilane Mix in a PP speed mixer cup. Then 94.87 g Omya BLH and 8.50 g Aerosil R202 were added and mixed in a mixer cup. Finally, 1 equivalent (128.80 g) of AATMP was added and mixed in a mixer cup. The mixture was then mixed in a speed mixer at 3500 rpm for 30 seconds to obtain an adhesive composition.

Comparative Example 1

0.2 eq (23.80 g) Jeffamine D230, 0.65 eq (37.11 g) 1,2-diaminocyclohexane, and 0.15 eq (44.06 g) Priamine 1071 were mixed in a PP speed mixer cup. Then 210.39 g Omya BLH and 23.38 g Aerosil R202 were added and mixed in a mixer cup. Finally, 1 equivalent (128.80 g) of AATMP was added and mixed in a mixer cup. The mixture was then mixed in a speed mixer at 3500 rpm for 30 seconds to obtain an adhesive composition.

Comparative Example 2

0.25 eq (29.75 g) Jeffamine D230, 0.65 eq (37.11 g) 1,2-diaminocyclohexane and 0.10 eq (7.85 g) Jeffamine EDR148 were mixed in a PP speed mixer cup. Then 183.16 g Omya BLH and 20.35 g Aerosil R202 were added and mixed in a mixer cup. Finally, 1 equivalent (128.80 g) of AATMP was added and mixed in a mixer cup. The mixture was then mixed in a speed mixer at 3500 rpm for 30 seconds to obtain an adhesive composition.

The obtained adhesive composition was tested for anchor strength and lap shear strength to various types of substrates. Results are presented in Table 1.

Table 1. Test results

In addition, the solvent resistance of the examples was also tested, and all inventive examples passed the test without showing any significant change after being rubbed with a paper tissue soaked in the solvent.

From Table 1, it is clear that the examples of the present invention exhibited excellent anchor strength and lap shear strength to various types of substrates, but the comparative examples could not achieve good adhesion performance in bonding plastics.

Claims (15)

A curable adhesive composition comprising:
multifunctional acetoacetate compounds,
polyoxypropylene polyamine, and
A polyoxyalkylene polyamine having an oxyalkylene unit selected from at least two of an oxypropylene unit, an oxyethylene unit, and an oxytetramethylene unit. The curable adhesive composition according to claim 1, wherein the multifunctional acetoacetate compound has at least 2 acetoacetoxy groups, preferably 2 to 10 acetoacetoxy groups, more preferably 3 to 4 acetoacetoxy groups. 3. The polyfunctional acetoacetate compound according to claim 1 or 2, wherein the polyfunctional acetoacetate compound is glycerol, trimethylolpropane, ethanol isosorbide, neopentylglycol, pentaerythritol, di-methylolpropane, di-pentaerythritol, propoxylated A curable adhesive composition that is an acetoacetylated polyol obtained from a monosaccharide, trimethylol ethane, and combinations thereof. 4. The curable adhesive composition according to any one of claims 1 to 3, wherein the polyoxypropylene polyamine is selected from polyoxypropylene diamine, polyoxypropylene triamine, and combinations thereof. The curable adhesive composition according to claim 4, wherein the polyoxypropylene diamine is represented by formula (1)

In the formula, x is 2 to 100, preferably 2 to 80. The curable adhesive composition according to claim 4, wherein the polyoxypropylene triamine is represented by formula (2)

In the formula, n is 0 to 6, w, y and z are each independently 1 to 100, more preferably 1 to 80, and the sum of w, y and z is 3 to 100, preferably 5 to 85, R ₁ is hydrogen or a linear or branched C ₁ to C ₁₆ alkyl group, preferably hydrogen or a linear or branched C ₁ to C ₈ alkyl group. The curable adhesive composition according to any one of claims 1 to 6, wherein the polyoxyalkylene polyamine has oxypropylene units and oxyethylene units, and preferably has a weight average molecular weight of 100 to 5,000, particularly 200 to 3,000. Curable adhesive composition according to any one of claims 1 to 7, wherein the polyoxyalkylene polyamine has oxypropylene units and oxytetramethylene units, and preferably has a weight average molecular weight of 100 to 5,000, in particular 200 to 3,000. . 9. The curable adhesive composition according to any one of claims 1 to 8, further comprising at least one amine cure accelerator according to formula (3):
R ² R ³ NH (3)
In the formula: R ² is hydrogen or a C ₁ -C ₆ alkyl group;
R ³ is a hydrocarbyl group having up to 36 carbon atoms containing an aromatic group, which hydrocarbyl group is optionally substituted with one or more -NHR ² groups, with one or more O atoms and/or with one or more -N(R ⁴ )-, wherein R ⁴ is a hydrogen atom; or,
R ³ is a C ₁ -C ₃₆ aliphatic group, optionally substituted with one or more -NHR ² groups, and optionally further interspersed with one or more O atoms and/or with one or more -N(R ⁴ )- groups, wherein R ⁴ is a hydrogen atom;
R ² and R ³ together with the N-atom to which they are attached may form a ring. 10. The method according to any one of claims 1 to 9, wherein the molar equivalent ratio of acetoacetate to amine in the curable adhesive composition ranges from 2:1 to 1:2, preferably ranges from 1.2:1 to 0.8:1, more preferably is a 1:1 curable adhesive composition. 11. The method according to any one of claims 1 to 10, wherein pigments, fillers, plasticizers, surface levelers, foam inhibitors, rheology modifiers, catalysts, antioxidants, tackifiers, adhesion promoters, flame retardants, UV-stabilizers and A curable adhesive composition optionally comprising one or more additives selected from combinations thereof. 12. The curable adhesive composition according to any one of claims 1 to 11, wherein the curable adhesive composition is free of a catalyst. A two-part curable adhesive composition comprising:
a first part comprising a multifunctional acetoacetate compound, and
A second part comprising a polyoxypropylene polyamine and a polyoxyalkylene polyamine having an oxyalkylene unit selected from at least two of an oxypropylene unit, an oxyethylene unit, and an oxytetramethylene unit. A cured product of the curable adhesive composition according to any one of claims 1 to 12 or the two-part curable adhesive composition according to claim 13. The curable adhesive composition according to any one of claims 1 to 12 or claim 13 for bonding a substrate made of or having a surface of paper, fabric, leather, metal, porcelain, porcelain, glass, wood, or plastic. Use of the two-part curable adhesive composition according to claim .